Treatment of aromatic hydrocarbon materials



M. P. MATusz'AK Filed nay 2s, 1945 TREATMENT OF AROMATIC HYDROCARBON MATERIALS CATALYST Sept. 245 1946.

R-E AcTANT's Patented sept. 24, 1946 TREATMENT AROMATIC HYDROCAON MATERIALS i y Maryan I. Matuszak, Bartlesville, Okla., assigner to Phillips Petroleum Company, a corporation y of Delaware Y Application May 26,1943, seria1No.-4s's,547

. 1 This invention relates to treatment of aromatic hydrocarbon materials and'more -particularlyrto the removalof organic uorine compounds Vand other undesirablelcompounds from such materials by 'treatment with liquid hydroiluoric acid. Thisv invention is a continuationin-part of my'copending application, Serial No. 395,282, 'filed May 26, 1941, now UnitedStates Patent 2,320,629, issued June l, 1943.

' In the synthesis of aromatic hydrocarbons by processes inwhich duerme-containing catalysts are used, small proportions of organic fluorinecontaining Icy-products are formed. Among such processes, one of the most important is the alkylation of aromatic hydrocarbons, such as benzene, toluene, and the like, with alkylating agents, such as olens, polar alkyl compounds', and the like, in the presence of catalysts comprising oneor vmore of such fluorine compounds as-hydrouoric acid, boron fluoride, and the like. Although the exactr nature of composition of the illumine-containing by-products has not been completely investigated, they are Vbelieved to be mostly alkyl and/or aryl uorides, such as may be derived from the valkylating agent and/or the original aromatic hydrocarbon. These byproducts are not completely removed by'washing the hydrocarbons with alkaline solutions. They tend to decompose at elevated temperatures, such as those employed in fractional `distillation of the hydrocarbons, thereby forming hydrouoric acid, which is corrosive, especially in the presence of moisture. y

In the afore-mentioned copendingapplication is disclosed treating of predominantly saturated hydrocarbon materials, specifically v-parain hydrocarbons, with. liquid hydrouoric acid to removeV organic fluorine compounds. It has now been `found that treatment of aromatic' hydrocarbon materials with liquid hydrouoric acidy elfects advantageous removal of organiefluorine compounds and of other compounds, such as alkylating agents, boron fluoride, and sulfur compounds. n y Y An object of this invention is to purify aromatic hydrocarbon materials.

Another object of this invention is to removev lundesirable organic* fluorine-contaning. compounds irom aromatic hydrocarbon materials.

OtherV objects and advantages will be apparentirom the followingr description, thela'c'com- Y pariyingfdrawing, and/or the.fappended claims.

fccording to Athis invention, yremoval of' organieiludrine compounds and other compounds tihatzare relatively highly soluble in hydrofluoric 25 Claims. (Cl. 26o-671) n acid from aromatic what upon hydrocarbon materials is eilected `by contacting the material in liquid phase with liquid anhydrous hydrouoric acid at a suitable temperature, vwhich may be between about .-100 and about 3506i', dependingy somethe* particular'materal, but which Vusually is 'optimally between about 20 and 100l F., separating the hydrouoric acid extract from the hydrocarbonrmaterial, and yfreeing the treated hydrocarbon material from a smallproportion of `dissolved hydrofluoric acid. The hydroiiuoric acid should .be used in suiflcientV amounty to form a distinctliquid acid phase; preferably it should be at least` several times this amount. The amount needed may vary with the content ofuorine-containing by-products, but the minimum'amount for any particular case may be readily found by trial; an amount between 20 and 100 per cent by volume of the hydrocarbon material is` generally satisfactormbut for high contents of fluorine-containing by-products, it may' greatly exceed 100 per cent. Because the mutual solubility of aromatic hydrocarbons and Y liquid hydrouoric acid increases appreciably with increase in temperature, elevated temperatures should usually be avoided; for example, the solubility of benzene in liquid hydroiluoric `acid increases from 2.0 weight per cent at 20 F.

to 5.0 Weight'per cent at 100 F. However, in some instances the treatment may be advantageously carried out at an elevated temperature,

after which, for improved mechanical separation of the hydrocarbon material and the acid, the

temperature may be lowered, say to a temperature in the range of 10 to 50 F. y

Separation of the acid andthe hydrocarbon phases is'usually eiected by gravitational settling, aided if' desired by cooling. Centrifugation may be used, but ordinarily it is not necessary.

Freeing of the treated hydrocarbon material from dissolved hydrouoric acid may be effected by various means, such asfdstilling, washing with Water or alkalinesolutions, contacting with metal salts or other compounds capable of combining with hydrogen fluoride, or thelike. However, it is 'generally advantageous to remove the dissolved hydrouoric acid by fractional distillation asl a low-boiling or azeotropic mixture with a low-boiling parafn having three to flve carbon atoms per molecule, preferably a butane. To this end, such a paraffin is added to Vthe hydrocarbon material before, during, or after d the contacting with liquidhydrofluorio acid, usually most advantageously after the acid phase E has been withdrawn from the hydrocarbon material. Because of its relative inertness, this parafn is preferably straight-chain rather than branched-chain. This paraffin forms a minimum-boiling azeotropic mixture with hydrofiuoric acid. Under the proper conditions, the overhead fraction obtained on fractional distillation is such an azeotropic mixture; however, in ac` tual plant practice, when close control is not feasible, the composition of the overhead fracposition of the azeotropic mixture at the pressure in use, although the process will have taken advantage of the principleinvolved. The lowboiling fraction carries with it, in the form of a low-boiling mixture, any hydroiiuoric acid remaining in solution in the hydrocarbon material, thereby eifecting removal of the dissolved acid without the loss of acid'that would occur if the removal were made by water-washing, alkaliwashing, or the like, and without the increase in temperature that would be necessary forremoval of the acid by simple fractional distillation. Simple fractional distillation of the dissolved hydrofluoric acid,l without prior addition of a low-boiling parafn, al'so'mayv be practiced- The acid removed by either type. of fractional distillation is generally suitable for refuse in the treatment of additional 'hydrocarbon material.

`Although the action of thehydroluoric acid is not completely understood atpresent,` it appears to` be due chiefly to a preferential solubility of organic fluorine compounds in the acid. Any procedure that effects an intimate contacting between the acid and the hydrocarbon phases, such as those well-known. inthe art of extracting with preferential solvents, is suitable. lUnduly pro-v longed contacting, in cases in which the acid may react slowly with the aromatic hydrocarbon to yield organic uorine com-pounds, should be avoided. The contactingr preferably should b'e effected in apparatus not subject to excessive attack by hydrofluoric acid.

As oleiin and nonolefin alkylating agents may react lwith hydrofl'uoric acid toV form organic Iuorine'compounds, the hydrocarbon materials to be treated by this process should be substantially free from alkylating agents. 'v However, relatively small proportions o-f unsaturated hydrocarbons or other'alkylating agents may be present, for-the, fluorine compounds formed by reaction with the acid are preferentially dissolved by the acid andare removed; in consequence, the treated material is freed not only from organic fiuorine compounds but also from unsaturated hydrocarbons and/or other alkylatingf agents. Similarly, many sulfur compounds are preferentially dissolved by the, acidV and are removed, so that the present process may be applied to the purification of sulfur-containing hydrocarbon materials.

'The hydroiluoric acid extract is usually passed to a catalytic hydrocarbon conversion lstep 'to be used as catalyst. When not so used it'is treated to recover the acid, which'is then re-used. In such a case, `sinceA this acid extract contains considerable dissolved varomatic hydrocarbon, it is preferably ,preliminarily extractedwith a lowboiling paraiinof three tofive carbon atoms per molecule, such as for example normal butanei The extraction is preferably made at a low temperature, such as approximately 30 to 60' which may be conveniently obtainedI by direct evaporative cooling, especially when thaparaiin is propane. The resulting paraffin extract is fractionally distilled torecover the aromatic hydro- "l tion may depart somewhat .from the exact Coincarbon material.

4 carbon, which is returned to the treated hydro- The propane-extracted acid extract is preferably also fractionally distilled, whereby the hydrofiuoric acid is recovered in an overhead fraction in condition suitable for re-use, and any undecomposed organic fluo-rine compounds are withdrawn in an oily kettle fraction. Understanding of some aspects of this invention may be facilitated by reference to the two figures of 'the accompanying exemplifying drawing, which are schematic flow diagrams illustrating specific embodiments of the invention for the treatment of aromatic hydrocarbons produced by alkylation in the presence. of a fluorine-containing catalyst. For the alkylation of benzene or toluene with an olefin or a nonprimary alcohol having three to five carbon atoms per molecule, this catalyst is suitablyhydrofluoric acid. For alkylation with ethylene, however, this catalyst is preferably, but n"ot necessarily, promoted by a minor proportion of boron fluoride, such as approximately l to 5 mol per cent.A Some benefit appears to result from the presence of a smallY proportion of moisture in the hydrofiuoric acid-boron fluoride catalyst; when an alcohol is the alkylating agent, water is formed as a ley-product of the alkylation.

In the embodiment of Figurev 1, the alkylation reactants enter the system by one or more inlets, represented by inlet i l controlled by valve I2. For the sake of simplicity, the reactants may be taken` to be benzene and ethylene, without. restricting the invention thereto. These reactants pass into alkylatorV 13 in which they are intle mately mixed with lthe catalyst, which enters the system through inletil controlled by valvey i0. As has been indicated, the catalyst may be different for different alkylating agents; in the present specific instance, it comprises substantially anhy-r drous hydrouoric acid and a minor proportion, usually about 3 mol per cent, of boron fluoride. Alkylator i3 may be any convenient reaction vessel having an agita'ting means and capable oi' withstanding the alkylating conditions; The reaction temperature may be broadly in thevrange of about 50 to about 400 F. The optimum temperature rangev differs for different alkylating agents, j being generally lower the higher, rthe number of carbon atoms in the alkylating agent; in the present specific instance, it is usually preferably in thefrange of to 200 F. lfThe pressure may be as high as isdesired, but it need be only sufcient to maintain substantially all of the reaction mixture in the liquid state. The average reaction time, or the time of .residence` of the hydrocarbon phase in the -alkylaton generally may vary in the range of abouti tolOO- minutes or more, depending upon the. other reaction conditions a time of 5 to l5 minutes, more specifically 10 minutes, is usually preferred. Conditions outside of theser ranges are suitable in some cases; the optimum conditions for any particular case may be readily determined by trial by oneskilled in the art. The mol ratio of benzene to` ethylene in the feed should be well in excess of 1;.1, preferably at least 10:1,` since the alkylation results generally improve with. increasey inthe benzeneto-,alkylating agent ratio. The proportion of catalyst preferably is in therange of about 0.2 to 4' times the 'weight of hydrocarbon in the 'reaction mixture. t

After a suitablecontact period, the resulting alkylation mixture is passed throughA conduit. l5 into` separator AI 6, in Awhich it 'is separated Vinto a The hydrocarbon phase is passed'through Valved conduitY I1 'into treaterv or extractor I8. yIls-.previously discussed a light (or flow-boilinglparafnysuch as.abutane,`ma'y be added tothe. aromatic hydrocarbon material -prior to its extraction with liquid hydrofluoric acid. If such an operation is practiced, a suitable amount of such a paran maybe addedthrough conduit 45 leading into conduit I1. The alkylation catalyst phase may be discharged in part or entirely from the systemthrough valved conduit 8, or itmay Abe recycled, at leastinpart, as by pump I9, through valved conduit 2D and acid-recycle conduit I4, back to a1ky1ator.I3;.hoWever, at least a part of it Vis preferably passed` through valved conduitr 2| into fractionator 22. InV this fractionator, the catalyst phase' is fractionally distilled into the f following. fractions; a fraction, comprising chiefly boron fluoride, hydrofluoric acid, and some lowboiling organic fluorine compounds, that is passed through valved conduit 23 intorecycle'conduit- I4, by which it is recycled to alkylator I3; a fraction, comprising chiefly hydrofluoric acid, that is passed through Aconduit 2'4 `'controlled by valveA 25 into extractor I8; and afraction, comprising unreacted benzene which was dissolved-inthe catalyst phase VandV acid-soluble .organic compoundsV of relatively high molecular weight, including some ilumine-containing compounds, that is withdrawn through outlet 28 controlled .by valve 21. "The unreacted benzene maybe recovered, as by fractional ,.distillation, and may be returned tothe system, by meansnot shown.

In extractor I8, the hydrocarbon phase enteringV fromconduit I1 is contacted in a countercurrent manner withthe hydrouoric acid` entering from conduit 24, whereby unreacted'alkylating agent, dissolved boron-fluoride, and organic uorine-cont'aining Icy-products of the alkylation step are removed from the -hydrocarbon phase, presumably' by preferential solution in the acid. Hydrofluori'c acidsufflcient to compensate for any losses occurring anywhere in the system mayA be added through inlet 28 controlledby valve129; if desired, his make-up acid may be advantageously added t0' extractor I8 at a point downstream, in the hydrocarbon stream, to the pointof entry of the hydrouoric acid from fractionator 22. Any losses of boron iiuoride are made up by additionr` of this promoter through inlet 9. y

`From extractor IB' lthe treated hydrocarbon material is forced, as by pump 30, through conduit 3I into Vfractionator 32, in which it is fractionally distilled into the following fractions: a relatively small light fraction that may be withdrawn through outlet 33 controlled by valve 34 but that usually Vis passed, at least in part,'to

alkylator I3, as .through conduit 35 controlled by valve 36, since it comprises chieyhydrofluoric acid that was carried in solutionrin the treated hydrocarbon material coming from the extractor AI8; a relatively` large medium `fraction vthat is practically acid-free and that is recycledV to alkylator I3, as through conduit 3'I controlled by valve 38, since it corx'ip'risesk chiey unrea'cted benzene; and -an alkylate kfraction comprising chiefly, in this specific embodiment, ethylbenzene, that is withdrawn.throughoutlet 3S controlled by valve 40 to .storage or. to additional processing steps, notl shown, such'asA concentration steps, dehydrogenation steps to convert ethylbenzene to styrene, or the like4 If it is desired to conduct this distillation in the presence of a light (or low-boiling) paraffin, as previously discussed, and such has not been. added through conduit 45, 'a

suitable amounty of such'a parain maybe added through conduit 46 leading into conduit 3|.

l. yFrom extractor I ithe hydrofluoric acid extract` isv preferably 'passed through rconduit 4 I controlled by'valveAZ'rv and .through recycle conduit I4 to alkylator I3;.to be used inthe alkylation step;

if desired, however, any part of the extract mayr the catalyst phase passed from the bottom of `extractor I8 may be passed through valved conduit 4 to extractor 5, wherein it is'contacted with a liquid, low-boiling paraiin, such as normal butane, introduced through conduit 6. The eX- tracted hydrofluoric acid, now relatively free of aromatic hydrocarbons, is passed through conduit 'I for rsuitable treatment, as discussed. The liquid extract, containing aromatic hydrocarbons andV some dissolved hydrogen uoride, is discharged through conduit 3 and, if desired,'may. be subjected tov distillation in suitable equipment, such. as illustrated by fractionatorr32.

In the embodiment .of .Figure 2, the alkylation reactants and thealkylation catalyst,which again forthe sake of 'simplicity may be taken'to be benzene and ethylene and hydrofluoric acidpromoted byboron fluoride, respectively, enter the system by one or more inlets, such as inlet 5I controlled by valve 52 and inlet 49 controlled by valve 53, respectively, into treating means .53. In

this means, the hydrocarbons pass generally upwardly through a lower, alkylator section 54 and then upwardly through an upper, extractor section `55. In the alkylator section they are intimately contacted in a generally countercurrent manner with the catalyst, which enters at least in part at thetop of the alkylator section from acid-recycle conduit 55, whereupon alkylation occurs. On-passing upwardly into and throughthe extractor section, the resulting hydrocarbon mixture is countercurrently contactedr with lsubstantially pure anhydrous hydrofluoric acid that enters the upperpart of the extractor rsection from conduit 5'I, whereupon organic uorine-containing by-products, boron fluoride, and unconsumed alkylating agents are removed from the hydrocarbon mixture. From the upper part of treating means 53, which extends .upwardly somewhat beyond extractor section 55 to preclude substantial entrainment of the acid phase, the extracted hydrocarbon mixture is forced as by pump 58, through conduit 59 into fractionator 60.

kThe hydrofluoric acid entering treating means 53 Afrom conduit 51 passes downwardly through extractor section 55 and then joins the catalytic material entering from conduit 56. AWhen the catalyst comprises boron fluoride, as in the present specific instance, the proportion of ,boron uoride entering through .inlet 49 is preferably s adjusted that the average composition, of the catalystin alkylator section 54 is that desired, such as for example l to 5 mol per cent of boron fluoride and to 99 mol per cent hydrouoric acid. When the catalyst is substantially pure hydroiluoric acid and does not comprise boro-n fluoride, as when the alkylating agent is relativelyA highly reactive or is an olefin .or nonprimary alcohol-z or three to i-lve carbon atoms per mole-V cule,y all fresh catalyst, namely hydroiiuoric acid, may enter. the system through inlet; 'I8` controlled byvalve. 19, in which case inlet lilY may be omitted or unused. Inl alkylator section- 54. thecatalyst. is intimately mixed with the alkylation mixture in any desired manner, but the general directionof the acid continues to be. downward, From the bottom of the alkylator` section, the acid orv catalyst phase isforced, as by pump 6l, through conduit 52, valve. 63, andxconduit 56back tothe top of the. alkylator section; however, instead of being thus. recycled to the alkylation step, any desired part, or all, of it may be, sent through valve 64. into fractionator 65 forl pur.- cation or reviv-cation, and ordinarily in commercial operationa part; is: so sent either continuously or intermittently,

In fractionator 65,` the acid phase is fractionally distilled into` the following fractions: a. fraction, comprising chiefly hydroiluoric, acid, boron fluoride, and some organic luorine compounds, that. is passed through conduit 6.5. controlled by valve 6.7. and through conduit 56f into alkylator section 54:. a fraction, comprising chiefly hydrofluoric: acid, that is` passed through valve 15 and conduit 51 into. the upper part of extractor section 55;. and a fraction, comprising benzene that was. dissolved in the acid phase and acid-soluble organic compounds of relatively high molecular weight, including some. iuorine-containing compounds, t'hat is` passed through. conduit 58 controlled by valve 6!A to` separator 15. In, separator 10;. this fraction is. heated to distill oli the benzene and to decomposev the iluorineV compounds to liberate. hydrofluoric acid; the; benzene and thehydrouoric acid are passed to alkylator section 54, as through conduit 'H controlled by valve '(2. The residual high-boiling material is Withdrawn from separator l). through outlet 13 controlled by Valve. '14.r

Hydroiiuoric acid sufficient in amount to compensate for any losses occurring anywhere, in the system is preferably added` through inlet 'I8 c ontrolled by valve 7:9; if desired, this make-up acid may be advantageously added to extractor section 5,5 ata point downstream, in the hydrocarbon stream, to the point of entry ofthe. hydrofluoric acid from fractionator 65.

In fractionator til, the extracted hydrocarbon mixture coming thereto through conduit 59 is fractionally distilled into the following fractions: a relatively small light fraction, comprising chiely hydroiluoric. acid, that may be withdrawn through outlet 8l!Y controlled by valve 8l but. that usually is recycled to some. suitable point in the system, asv by being passed through conduit 82A controlled by valve 83 into conduit. 55 and thence to alkylator section 54; a relatively large medium fraction, comprising chiefly practically acid-free benzene, that is recycled through valve 84 and conduit 85 to alkylator section 54; and an alkylate` fraction, chieily ethylbenzene, that is withdrawn through outlet 85 controlled by valve 81- to. storage or to additional processing steps,l not shown.

In the embodiments of; Figures 1 and 2, all of the hydrocarbon mixture resulting from the alkylation step is shown to be extracted with hydrofluoric acid. Extraction of all of this hydrocarbon mixture, however, is noty always neces,- sary; in fact, certain advantages follow if only the actual alkylate is so extracted. Thus, after the al'kylation step and after separation of the hydrocarbon phase from the acid phaseLthe. hy-

drocarbon phase. may be passed into a. fractionator,.not;shown, in. whichit: is separatedinto two fractions. TheI light fraction, which comprises the unreacted benzene, the catalytic. material dissolved inv theV hydrocarbon phase. and some of theY organicfluorine compounds, is returned to` the. alkylation. stepr, the, alkylate fraction is exftracted with, liquid hydrofluoric acid. to. remove; the residua-l` organic luorine compounds, and is then freed from dissolved hydroiluorie acidv in yaccordance with the description already given.r The hydrouoric acid extract is preferably sent to the alkylation step, but if desired part or all of' it may be passed into a fractionator, in which it is freedV by fractional distillation from higherboiling. organic compounds and from which, it may be returned to the extraction step or senttQ the, alkylation. step. The hydroiuoric acid phase separated from theA alkylation mixture may be. recycled directly to the alkylation. sten,v or. part or all of it may be similarly fractionally distilled in the same or a differentfractionator, from which it. may be returned to the alkylation step; or seht to the extraction step, asis desired.

The hydrofluoric acid used in the extraction should be concentrated, and in some instances may be substantially anhydrous. Generally any small',` fortuitous. amount of waterwill not be deleterious, and at times it may be desirable to ensure the presence Ofa few-per centof Water. In nearly all cases, however, concentrated hydroluoric acid will refer to acid having; a strength greater than 90.. per cent, and most generally greater than 95 per cent. The same will be truc for the hydroiiuoric acid used. for alkylation,

By fractionator, as. used in this; specification, is meant any system of` fractional-distillation devices. that will eiect the results indicated; it may consist of one. or more than one fractionating column, as is found to be. necessary or desirable forV any particular case in accordance with. the. well-known art of fractional` distillation, Many other well-known devices not specifically shown or described in this specification, which are kno-wn to contributey to or improve the attainmentorl the. results indicated herein, may be incorporated or used without passing beyond the scope of this, invention or the. spirit of' this dis-Y closure.

Some aspects of the invention atei further, illllS- trated; bythe following examples, which should not, however, be construed as necessarily limiting the invention. i

55 Example I Benzene. was alkylated with propylene in a s ma-ll continuous pilot plant. comprising a 7450 cc. reactor having a` 1725 R. P. M. turbomixer. The catalyst was anhydrous hydrouoric acid; the volume ratio of hydrocarbons to catalyst in the reactor wasmaintained at 1.3:1. The mol ratio of. benzene to. propylene in the feed was 83:1. The temperature was 118" F.; the time of residenceof the hydrocarbon phase in the reactor was 20.3 minutes. The yield of total alkyla-tewas 249 perY cent by weight of the propylene. The total alkylate contained 93.5 per cent by volume ofisopropylbenzene, 5.5 per cent. of diisopropylbenzene, and 1.0 per` cent of heavier product. The isopropylbenzene fraction contained 0.0059. per cent byV weight of organic iiucrine. and 0.0117 per cent byv weight vof organic sulfur. I

When. such an isopropylbenzene fraction is 75 countercurrently extracted with, approXimatehfY a third of its lovvn volume of anhydrous hydrofluoric acid, the organic ilu'orinegand sulfur are substantially -completely `removed, therebyA improv,- ing the isopropylbenzene for use `as van'ingredient in high-octane aviation fuel. "Because of 'the relatively high proportion of sulfur, theresulting hydrofluoric acid extract is preferablypreliminarily freed from most of its contentiofv sulfur compounds, Which are relatively higheboiling, by

fractional distillation, before itis ,passed tothe alkylation step. Y

Example II Benzene is alkylated with ethylene in the preslence fof an approximately equal volume of hydroh rently extracted With-substantially pure anhydrous hydrofluoric acid, whereby it is freed from ja small proportion of dissolved boron fluoride and organic iiuorine, compounds, among which `is ethyl fluoride- The extracted hydrocarbon phase is freedifrom dissolvedy hydrofluoric acid,

,as by`addition of normal butane anddistillation of the butane and the hydrofluoricv acid as a lowboiling mixture; it is thenv f-ractionally distilled to isolate Vthe fluorine-iree ethylbenzene. The jacid extract is fortified by the addition of enough boron fluoride to make the total content of this compound approximately 3 mol rper cent, and .the fortified acid is passed to the alkylation step to be used as the catalyst for ethyltion of addi tional benzene. f

An especially useful specific application of the invention is in the manufacture of ethylbenzene,

which is useful as an ingredient in aviation fuel v Yand which is readily dehydrogenated to Vstyrene for use in the manufacture of synthetic rubber. The alkylation of benzene with ethylene requires more or less drastic or adverse conditions, such as a reaction temperature appreciably aboveV room temperature. Undersuch drastic Yor-adverse con,-

.ditions, the alkylation tends to give .a vproduct containing a relativelyhigh `proportion of un-reacted alkylating agent, heavy unsaturatedhy.- drocarbons, andorganic ilumine-containing compounds -such as alkyl fluorides and complex addition' products of the alkylating agent with the catalyst'. rExtraction of the product, `either before or after the separation from the unreacted benzene', with hydroiluoricv acid accordance with this invention effects an excellent removal of these materials, thereby improving'the quality ofthe alkylation product.

Because the invention may be practiced other- Wise than as specifically illustrated and described, and because many modifications and variations within the spirit and scope of the invention Will be obvious` to those skilled inthe art, the inven- -tien should not be unduly restricted by the foregoing specication. l

I claim:

1. A process for the removal of organic fluorine compounds from aromatic hydrocarbon materials containing the same, which comprises contacting such a hydrocarbon material with liquid hydrofluoric acid, correlating the relative amounts Vof said hydrocarbon and hydrofluoric acid andthe lliquid hydroiluoric acid phase, separating the tre- "sulting hydroiiuoric acid Vextract ."from thehydroi- Adissolved hydroiluoric acid.

2. A process for the removal of organic''luorine compoundsv from aromatic hydrocarbon materials containing the same, which vcomprises contacting such a hydrocarbon material with liquidhydrofluoric acid, correlating the relative .amounts of saidhydrocarbon and hydrofluoric acid and :the temperature of contacting so as to insure `the presence cfa liquid hydrocarbon phase 'and'of a liquid'hydroiuoric acid phase, V'separating the resulting hydrofluo-ric acid extract .from the-hy; ,drocarbon material, and distilling fromfthevfextracted hydrocarbon material any residual,y jdissolved hydroiiuoric acid.y

v3. A process of treating aromatic hydrocarbon material containing vorganic fluorine compounds, which comprises adding to said materia-1 an rap- 'preciable fraction of its own volume of a para'in having three to five carbon atoms per molecule,

drocarbon material Yfrom 'the added paraffin and from dissolved hydrofluoric acid by fractional distillation.

4. A process loftreating an aromatic hyd-ro# f carbon material containing organic' fluor-ine :com--` pounds, which comprises contacting' said hydrocarbon material with vliquid hydroliuoric lacid, correlating the relative amounts of'sa-idr hydrolcarbon and hydrolluoric acid and the temperature of contacting so as to insure the Vpresence of a liquid hydrocarbonphase and of a liquid hydroiluoric acid phase, separating the resulting Vhydrofluoric` acid extract Vfrom the hydrocarbon material, adding to Athe lextractedA :hydrocarbon material an appreciable amount Yof a vliqueiled Aparaffin having three to yfive carbon atoms 'per y molecule, andy fractionally distilling the resultt temperature of contacting so as to insurev r:the

Vpresence of 'a liquid hydrocarbon phase and-'of a ing'mixture to remove the addedparafznfand the hydrofluoricacid remaining dissolved-in the hydrocarbon material. I f I k 5. The process of claim 4, in Whichjthe. .ad-ded Vparaflin is normal butane.

k6. The process of claim v1, in which ther-mixture of hydrocarbon material and hydrofluoric acid is contacted at a temperature in the range of 10 to 50"k F. prior to the separationY of the .hydroiluoric acid extract. I v

7. The process 'of claim 1, `in which said aroy matic hydrocarbon material is at least a part of a, hydrocarbon mixture produced in the lpresence of a catalyst comprising at least one fluorinacontaining compound. n

8. The process of claim 1, in which said aromatic hydrocarbon material is at least par't of the hydrocarbon mixture resulting from alkyl'ation of at least one aromatic hydrocarbon 'in thepresence of Ya catalyst comprising at least one fluorine-co'ntaining compound. N

9."The process of claim 1, in which said varo'- matic hydrocarbon material is vat least 'a Daft of the hydrocarbon mixture resulting from 'alkylation of at least one aromatic hydrocarbon'in the presence of hydrofluoric acid las alkylation 10. The process of claim 1, in which said aromatic hydrocarbon material is at least a part of the hydrocarbon mixture resulting from alkylation of benzene in the presence of a catalyst comprising a major proportion of hydrofluoric acid and a minor proportion of boron fluoride.

11. The process of claim l, in which said contacting is countercurrent.

12. The process of claim l, in which said aromatic hydrocarbon material is at least a part of the hydrocarbon mixture resulting from alkylation of at least one aromatic hydrocarbon in the presence of a catalyst comprising a major proportion of hydrofluoric acid and a minor proportion of boron fluoride, and in which said hydrouoric acid extract is used as at least a part of the catalyst for the production of additional hydrocarbon material.

13. In a process of alkylating an aromatic hydrocarbon with an alkylating agent selected from the group consisting of oleins having two to five carbon atoms and of polar nonprimary alkyl compounds having three to ve carbon atoms in atleast one nonprimary alkyl group in the presence of a fiuorine-containing catalyst, the improvement which comprises extracting at least a part of the resulting alkylation hydrocarbon product with substantially pure liquid hydroi'luoric acid for a time that is suiiicient for eiecting substantial removal of organic uorne-containing by-products of the alkylation.

14E In a process of alkylating benzene with ethylene in the presence. of a catalyst comprising a major proportion of hydrofluoric acid and a minor proportion of boron iiuoride, the improvement which comprises extracting at least a part of the resulting alkylation hydrocarbon product with concentrated relatively pure liquid hydrofluoric acid for a time that is sufficient for effecting substantial removal of organic luorine- Ycontaining by-products of the alkylation.

15. In a process of alkylating an aromatic hydrocarbon with an alkylating agent in the presence of a iluorine-containing catalyst, the improvement which comprises extracting the alkylation product with liquid hydroiluoric acid.

16. A process of purifying an aromatic hydrocarbon material containing organic fluorine and sulfur compounds which comprises removing said organic iluorine and sulfur compounds by liquidphase extraction with substantially purehydrofluoric acid.

17. In a process for the alkylation of an aro-Y matic hydrocarbon in the presence of a catalyst containing a major proportion of hydrouoric acid and a minor proportion of boron fluoride, wherein the alkylate contains organic fluorine compounds, the improvement which comprises contacting in liquid phase a hydrocarbon fraction containing an alkylate from thealkylation step with concentrated liquid hydrouoric acid under conditions such that there is a negligible amount of reaction of hydrocarbons catalyzed by said hydrofluoric acid and such that there is a reduction in the content of organic iluorine compounds in said hydrocarbon fraction, separating a hydrocarbon phase and a hydrofluoric acid phase, passing at least a portion of said hydrouoric acid phase as catalyst to an alkylation step for producing said alkylate, and removing dissolved hydrouoric acid from said hydrocarbon phase.

18. An improved process for the alkylation of an aromatic hydrocarbon, which comprises al- 12 kylating an alkylatable aromatic hydrocarbon in the presence of a liquid'alkylation catalyst comprising hydroiluoric acid, passing a. resulting mixture of hydrocarbons and catalyst to separating means, separating a hydrocarbon liquid phase from said liquid catalyst, contacting said hydrocarbon liquid phase with substantially pure concentrated liquid hydroiluoric acid to eiect a purification of said hydrocarbon phase, passing liquid hydroiluoric acid eiiluent from said contacting to said alkylation, and removing dissolved hydroiluoric acid from a hydrocarbon phase eilluent from said contacting.

19. The process of claim 18, in which said catalyst is hydroiiuoric acid promoted with approximately 1 to 5 mol per cent of boron fluoride.

20. An improved process for the alkylation of an aromatic hydrocarbon, which comprises passing a liquid mixture of an alkylatable aromatic hydrocarbon and an alkylating agent 'to the lower part of a treating means comprising a lower alkylating Zone and an upper extracting zone, passing to the upper part of said alkylating zone a liquid catalyst comprising recycled catalytic material and hydrouoric acid from said extracting zone as hereinafter recited, intimately and countercurrently contacting said liquid mixture in said alkylating zone with said liquid catalyst under alkylating conditions to,effect alkylation of said aromatic hydrocarbon, withdrawing from the bottom of said treating means liquid catalyst effluent from said alkylating zone and passing a portion of said catalyst as said recycled catalytic material to said treating means at an intermediate part between said extracting 'zone and said alkylating zone, passing substantially pure concentrated liquid hydrorluoric acid to an upper part of said extracting zone, pass- 'alkylatingqzona passing the resulting extracted 'hydrocarbon mixture from the top of said extracting zone and from the top of said treating means, andrecovering therefrom alkylated aromatic hydrocarbons so produced.

2l. A process for the removal of organic iiuorine compounds from an laromatic hydrocarbon material vcontaining the same as an impurity, which comprises contacting such an aromatic hydrocarbon material with liquid hydrofluoric acid, correlating the relative amounts of said hydrocarbon material and said hydrouoric acid and the temperature of contacting so as to insure the presence of a liquid hydrocarbon phase and a liquid hydrofluoric acid phase, separating the resulting hydrofluoric acid extract from the aromatic hydrocarbon material, contacting said extract with a liquid paraiin hydrocarbon having three to five carbon atoms permolecule under conditions of temperature and relative proportions such as to insure the presence of separate liquid hydrocarbon and hydrofluoric acid phases, separating the resulting hydrocarbon extract, and subjecting both said extracted aromatic hydrocarbon material and said hydrocarbon extract to fractional distillation to recover relatively fluorine-free aromatic` hydrocarbon materials.

A22. The process of claim 2l in which each said contacting step is conducted ata temperature .between about 20 and 100 F.

23. A process for the removal of organlc sulfur compounds from an aromatic hydrocarbon material containing the same as yan impurity, which comprises contacting such an aromatic hydrocarbon materialwith liquid hydroluoric acid, correlating the relative amounts of said hydrocarbon material and saidhydrofluoric acid andy Y 114 y Y conditions of temperature and relative proportions such as to insure the presence of separate 'liquidhydrocarbon and hydroiiuoric acid phases,

separating the resultingv hydrocarbon extract, Y .and subjecting both said extracted aromatic hydrocarbon material andsaid hydrocarbon extract tok fractional distillation to recover relatively sul fur-free aromatic hydrocarbon materials.

24. The process of claim 2 in which said conu tacting is conductedat a temperature between about 20 and 100 F.

25. The process of claim 23 in which said extraction is conducted at a temperature between about 2o and 100 F. l

l MARYAN P. MATUSZAK. 

